Phenyl- and naphthyl-glyoxylonitrile oximino carbamates for the protection of crops against injury by herbicides

ABSTRACT

Oxime carbamates and oxime carbonates of the formula ##STR1## in which Ar is optionally substituted phenyl, naphthyl, furan or thiophene, 
     X is hydrogen, carboxylic acid, alkanoyl, halogen or alkyl, and 
     R is a mono- or di-substituted amine, an optionally substituted alkoxy or an optionally substituted alkylthio group, the substituents of which include optionally-substituted hydrocarbyl groups and heterocyclic groups, 
     are suitable as antidotes for the protection of cultivated plants against harmful agricultural chemicals, in particular against herbicides which are insufficiently compatible with the cultivated plants. These compounds can be used either on their own or together with the agricultural chemicals. One of the possibilities offered is the dressing or immersion treatment of seed or of seedlings, of the crop to be protected, with solutions or dispersions of said compounds.

This is a division of application Ser. No. 112,049 filed on Jan. 14,1980, U.S. Pat. No. 4,416,686 which is a continuation of applicationSer. No. 938,205, filed on Aug. 30, 1978, now abandoned.

The present invention relates to oxime carbamates and oxime carbonatesof the general formula I ##STR2## to novel compositions based on thesecompounds, and to the application of these compositions or compounds forthe protection of cultivated plants against harmful agriculturalchemicals.

The symbols in the formula I have the following meanings:

Ar is a phenyl group of the formula ##STR3## a naphthyl group which issubstituted by R₂ and R₃, a furan or thiophene ring which isunsubstituted or substituted by halogen, NO₂ or lower alkyl, or Ar isone of the radicals --COOR₄ or --CO--R₈,

X is --CN, lower alkanoyl, a carboxylic acid ester group, --COOH,hydrogen, a carboxylic acid amide group, halogen or lower alkyl,

R₁ is hydrogen, halogen, lower alkyl, lower alkoxy, or a phenoxy groupwhich is in the para-position and which is unsubstituted or substituteda maximum of twice by halogen, --CN, NO₂ or CF₃,

R₂ and R₃ independently of one another are hydrogen, halogen, NO₂, loweralkyl, haloalkyl or lower alkoxy,

R₄ is an aliphatic, cycloaliphatic or araliphatic group, and an aromaticradical can be substituted as defined under R₂ and R₃ and can beadditionally substituted by --CN,

R is either

(a) a radical --N(R₅)(R₆), in which R₅ is lower alkoxy or is the same asR₆, R₆ is hydrogen or an aliphatic, cycloaliphatic, araliphatic,aromatic or heterocyclic group, and an aromatic radical can besubstituted as given under R₂ and R₃, or

(b) a radical --YR₇, in which Y is oxygen or sulfur, and R₇ is one ofthe 5 groups given for R₆,

R₈ is either

(a) a radical --N(R₉)(R₁₀), in which R₉ is hydrogen, lower alkyl orcycloalkyl, and R₁₀ has the meaning of R₆ or is hydrogen, or R₉ and R₁₀together with the --N atom form a 3-7-membered ring which can besubstituted by lower alkyl groups, or

(b) a radical --NH--CONHR₁₀.

Compounds of the formula I are accordingly (a) carbamates or (b) (thio)carbonates.

Halogen in the formula I is fluorine, chlorine, bromine or iodine.

Carboxylic acid esters are carboxylic acid lower alkyl esters.Carboxylic acid amides denote, besides --CONH₂, alsomonoalkyl-substituted or symmetrically or unsymmetricallydialkyl-substituted amides, with the alkyl groups being lower alkyl.

The term `alkyl` on its own or as part of a substituent includesbranched and unbranched C₁ to C₈ alkyl groups; lower alkyl denotes C₁-C₄ alkyl. Examples are methyl, ethyl, propyl, isopropyl, butyl,isobutyl, sec-butyl and tert-butyl, and also the higher homologues amyl,isoamyl, hexyl, heptyl or octyl, together with isomers thereof.Correspondingly, alkanoyls or cyanalkyls contain an additional C atom.

The term `aliphatic group` includes radicals which are saturated(alkyls) and also unsaturated (alkenyls, alkadienyls or alkynyls), whichare halogen-substituted, cyano-substituted and interrupted by oxygen,and which contain a maximum of 8 carbon atoms. The term `aromatic group`in the definition of the substituents R₄, R₅ and R₆ embraces phenyl andnaphthyl. The term `araliphatic radical` is to be interpreted inaccordance with the two preceding definitions. An araliphatic radicalincludes an aryl group such as unsubstituted or mono- to tri-substitutedphenyl, or naphthyl, which is bound by way of lower alkyl or loweralkenyl to the radical of the molecule. Examples are benzyl, phenethylor phenylallyl and also homologues.

The term `heterocyclic radical` includes 5- to 10-membered ring systemshaving 1 to 2 rings and a maximum of 3 heteroatoms from the series N, Oor S. C₃ -C₇ cycloalkyl groups are cyclopropyl, cyclobutyl, cyclopentyl,cyclohexyl and cycloheptyl. Cycloaliphatic radicals correspond to thesering systems, but in addition they may contain, if structurallypossible, one or more double bonds.

The arylglyoxylnitrile oximes of the general formula ##STR4## suggestedin the U.S. Pat. No. 3,799,757, are insufficiently effective as growthinhibitors and plant-growth regulators; furthermore, they are not stableand decompose after a fairly short space of time. No herbicidal-antidoteaction has become known.

In comparison with the above compounds, oximes of the formula I areexcellently suitable for protecting cultivated plants, such ascultivated millet, rice, maize, varieties of cereals (wheat, rye, barleyor oats), cotton, sugar beet, sugar cane, soya bean, etc., from beingattacked by agricultural chemicals harmful to plants, particularly byherbicides of the most varied classes of substances, such as triazines,phenylurea derivatives, carbamates, thiolcarbamates, haloacetanilides,halophenoxyacetic acid esters, substituted phenoxyphenoxyacetates andphenoxyphenoxypropionates, substituted pyridineoxyphenoxyacetates andpyridineoxyphenoxypropionates, benzoic acid derivatives, and so forth,in cases where these chemicals do no act selectively or do not actsufficiently selectively, that is to say, damage to a greater or lesserextent the cultivated plants in addition to destroying the weeds to becontrolled. The invention relates also to compositions which containthese oxime derivatives of the formula I, together with herbicides.

There have already been suggested as antidotes various substances ableto specifically antagonise the harmful action of a herbicide on thecultivated plant, that is to say, able to protect the cultivated plantwithout noticeably affecting the herbicidal action against the weeds tobe controlled. Depending on its properties, as antidote of this kind(also called a safener) can be used for the preliminary treatment of theseed of the cultivated plant (dressing of the seed or of the seedlings);or it can be applied into the seed furrows before sowing; or it can beapplied as a tank mixture, on its own or together with the herbicide,before or after emergence of the plants. The pre-emergence treatmentincludes both the treatment of the cultivated area before sowing(ppi=pre plant incorporation) and the treatment of the sown cultivatedarea before emergence of the plants.

Thus, the British Patent Specification No. 1,277,557 describes thetreatment of seed and seedlings of wheat and sorghum with certain estersand amides of oxamic acid before the attack byN-methoxymethyl-2',6'-diethylchloroacetanilide (Alachlor). Otherpublications (German Offenlegungsschriften Nos. 1,952,910 and 2,245,471,and French Patent Specification No. 2,021,611) suggest antidotes for thetreatment of cereals, maize seed and rice seed to protect them againstattack from herbicidal thiolcarbamates. In the German PatentSpecification No. 1,576,676 and U.S. Pat. No. 3,131,509,hydroxyaminoacetanilides and hydantoins are suggested for the protectionof cereal seeds against carbamates, such as IPC, CIPC, and so forth. Infurther development, however, all these preparations have proved to beinadequate.

To be emphasised as antidotes are in particular those compounds of theformula I in which Ar is a phenyl or naphthyl radical as defined in theforegoing, and the other substituents have the following meanings: X iscyano, hydrogen, lower alkanoyl, a carboxylic acid ester group, acarboxylic acid amide group or lower alkyl, R₁ is hydrogen, halogen, ora phenoxy group which is in the para-position and which is unsubstitutedor substituted a maximum of twice by halogen, --CN or CF₃, R₂ and R₃independently of one another are hydrogen, halogen, lower alkyl,haloalkyl or lower alkoxy, whilst Y and R₅, R₆ and R₇ have the meaningsalready defined. This subgroup is to be called compound group Ia.

Amongst these compounds of the group Ia, the group Ib constitutes one ofthe compound groups preferred as antidotes. Compounds of the group Ibare those of the formula I in which Ar is a phenyl group as defined inthe foregoing, X is cyano, hydrogen, acetyl, --COO-lower alkyl,--COONH₂, --COONH-lower alkyl, --COON (lower alkyl)₂ or methyl, R₁ ishydrogen, R₂ and R₃ are hydrogen, halogen, lower alkyl, CF₃, methoxy orethoxy, R₅ is hydrogen, lower alkyl or lower alkoxy, R₆ is an aliphaticgroup, or a phenyl group which is unsubstituted or substituted byhalogen, lower alkyl, CF₃, methoxy or ethoxy, Y is oxygen or sulfur, andR₇ has the meaning given above for R₆.

An important group of antidotes is formed by those compounds of theformula I in which Ar is a thiophene ring unsubstituted or substitutedby halogen or lower alkyl, and in which the substituents X, Y, R₅, R₆and R₇ have the meanings given for the compound group Ia, but preferablythe meanings given for the compound group Ib.

A further important group of antidotes for the protection of cultivatedplants against herbicides is the subgroup of the formula I in which Aris one of the radicals --COOR₄ or --COR₈, wherein R₄ is a loweraliphatic group having a maximum of 4 C atoms or is phenyl, and in thedefinition of R₈ the substituents R₉ and R₁₀ independently of oneanother are hydrogen or lower alkyl, or phenyl unsubstituted orsubstituted by halogen, CF₃ or lower alkyl, whilst the substituents X,Y, R₅, R₆ and R₇ have the meanings given for the compound group Ia, butpreferably have the meanings given for the compound group Ib.

Surprisingly, oximes of the formula I have the property of being able toprotect cultivated plants against attack from agricultural chemicalsharmful to plants, particularly against herbicides of the most variedclasses of substances, including 1,3,5-triazines, 1,2,4-triazinones,phenylurea derivatives, carbamates, thiolcarbamates, phenoxyacetates,phenoxypropionates, haloacetanilides, halophenoxyacetates, substitutedphenoxyphenoxyacetates and phenoxyphenoxypropionates, substitutedpyridinephenoxyacetates and pyridinephenoxypropionates, benzoic acidderivatives, and so forth, in cases where these chemicals are notcompatible, or not sufficiently compatible, with the cultivated plants.

Depending on the purpose of application, such an antidote of the formulaI can be used for pretreatment of the seed of the cultivated plant(dressing of the seed or of the seedlings), or can be applied to thesoil before or after sowing, or can be applied on its own or togetherwith the herbicide before or after emergence of the plants. Thetreatment of the plant or of the seed with the antidote can therefore becarried out essentially independently of the point of time ofapplication of the phytotoxic chemicals. It can however be carried outalso simultaneously (tank mixture). Pre-emergence treatment includesboth the treatment of the cultivated area before sowing (ppi=pre plantincorporation) and the treatment of the sown area before emergence ofthe plants.

The applied amounts of the antidote in proportion to the amounts ofherbicide depend largely on the type of application. If a fieldtreatment is undertaken, the amounts of antidote of the formula I withrespect to amounts of the phytotoxic chemical are in the ratio of 1:100to 5:1, preferably 1:20 to 1:1. In the case of seed dressing and similarspecific protective measures, much smaller amounts of antidote arerequired however compared with the amounts of herbicide employed forexample later per hectare of cultivated area (for example about 1:3000to 1:1000). There is as a rule only a loose connection betweenprotective measures, such as seed dressing with an antidote of theformula I, and a possible subsequent field treatment with agriculturalchemicals. Pretreated seed and plant material can later come intocontact, in agriculture, horticulture and forestry, with a variety ofchemicals.

The invention relates therefore also to compositions for protectingcultivated plants, which compositions contain as active substance anantidote of the formula I together with customary carriers. Compositionsof this type can optionally be additionally mixed with thoseagricultural chemicals having an effect from which the cultivated plantis to be protected, for example they can be mixed with a herbicide.

Within the scope of the present invention, cultivated plants are allplants which produce in some form useful materials (seeds, roots,stalks, tubers, leaves, blossom, and components such as oils, sugar,starch, protein, and so forth), and which are cultivated and attended tofor this purpose. These plants include for example all varieties ofcereals, maize, rice, cultivated millet, soya bean, beans, peas,potatoes, vegetables, cotton, sugar beet, sugar cane, peanuts, tobaccoand hops, and also ornamental plants, fruit trees as well as banana,cocoa and natural rubber plants. This list of plant types does notconstitute any limitation. An antidote can as a rule be used everywherewhere a cultivated plant has to be protected against the phytotoxicityof a chemical.

Compounds of the formula can be produced from the free oximes by severalprocesses, which are shown in schematic form in the following: ##STR5##

(In the preceding diagrams, Na represents sodium or another alkalimetal).

Suitable for obtaining compounds of the formula I are essentially allsolvents which behave inertly under the conditions of the reaction. Forexample, hydrocarbons, particularly however polar solvents such asacetonitrile, dioxane, cellosolve or DMF, and also ketones such asmethyl ethyl ketone, acetone, and so forth. Solvents containing hydroxylgroups are excluded.

The temperatures are within the range of -10° C. to about 150° C.,preferably between 20° and 120° C.

As agents splitting off hydrogen halide, it is possible to use bases,such as tert. amines (triethylamine, triethylenediamine, piperidine, andso forth). Also a suspension of sodium carbonate in an anhydrousreaction medium suffices in some cases. Oximes are present in twostereoisomeric forms, the syn and anti form. By `compounds of theformula I` are accordingly meant, within the scope of the presentspecification, both stereoisomeric forms, on their own or as mixtureswith each other in any reciprocal mixture ratio.

The Examples which follow illustrate the production of the novel oximesof the formula I. Temperature values are given in degrees Centigrade.

EXAMPLE 1 ##STR6##

23.5 g (0.16 mol) of benzyl cyanide oxime is placed into 100 ml ofacetonitrile. After 25 ml of methylisocyanate and a small, catalyticallyacting, amount of diazabicyclooctane have been added, the reactionmixture is heated to 50° C., and the final product precipitates after ashort period of time. It is allowed to stand overnight, and is thenfiltered off with suction, washed with acetonitrile, and subsequentlydried at 60° with hexane to yield 29.2 g (=89.8% of theory) of finalproduct having a melting point of 172°-175° C.

EXAMPLE 2 ##STR7##

14.6 g (0.1 mol) of benzykl cyanide oxime is placed into 100 ml ofacetonitrile; there are then added 18.7 g (0.1 mol) of3-trifluoromethylphenylisocyanate and a, catalytically acting, smallamount of diazabicyclooctane. The reaction commences immediately,whereupon the reaction mixture heats up to about 50°. it is stirred on awater bath for a further 4 hours; the final product which hasprecipitated is then filtered off with suction, washed withacetonitrile, and dried in vacuo at 50° to yield 25.5 g of final producthaving a melting point of 172°-173°.

EXAMPLE 3 ##STR8##

6.3 g (0.05 mole) of chlorothioformic acid-S-ethyl ester is addeddropwise to a mixture of 11.9 g (0.05 mole) of the sodium salt of3,4-dichlorobenzyl cyanide oxime in 50 ml of acetonitrile. The reactionmixture is then heated, refluxed for 4 hours and concentrated in vacuo.Methylene chloride is added to the residue, and the mixture is stirredwith active charcoal and filtered. The filtrate is concentrated byevaporation to yield 11.2 g (=73.7% of theory) of the final product inthe form of oil.

EXAMPLE 4 ##STR9##

14.2 g (0.1 mol) of cyanoacetic acid ethyl ester oxime is placed into100 ml of acetonitrile in a flask fitted with stirrer. A solution of15.3 g of p-chlorophenylisocyanate in 20 ml of acetonitrile is addeddropwise with stirring, and the reaction mixture is stirred for 5 hoursat 60°-70°. The solution is afterwards filtered hot and the filtrate iscooled in ice water. The final product which has crystallized out isfiltered off, washed with acetonitrile/hexane and dried; it has amelting point of 147°-148° C. In this manner or by one of theaforementioned methods, there can be produced the following carbamatesof the formula:

    __________________________________________________________________________     ##STR10##                                                                    Comp.                          Physical                                       No. R.sub.1                                                                            R.sub.2                                                                              R.sub.5                                                                          R.sub.6     constants                                      __________________________________________________________________________    1   H    H      H  CH.sub.3    m.p. 172-175°                           2   H    H      H  C.sub.2 H.sub.5                                                                           m.p. 93-96°                             3   H    H      H  n-C.sub.3 H.sub.7                                                                         m.p. 89-91°                             4   H    H      H  isoC.sub.3 H.sub.7                                                                        m.p. 92-94°                             5   H    H      H  n-C.sub. 4 H.sub.9                                                                        m.p. 98-101°                            6   H    H      H  tert.C.sub.4 H.sub.9                                                                      solid                                          7   H    H      H  CH.sub.2 CH.sub.2Cl                                                                       m.p. 138-141°                           8   H    H      H  CH.sub.2OCH.sub.3                                          9   H    H      H                                                                                 ##STR11##                                                 10  H    4-Cl   H  n-C.sub.4 H.sub.9                                                                         m.p. 124-126°                           11  H    4-Cl   H  CH.sub.2OCH.sub.3                                                                         m.p. 110-114°                           12  H    4-Cl   H  tert.C.sub.4 H.sub.9                                                                      m.p. 102-105°                           13  H    4-Cl   H  isoC.sub.3 H.sub.7                                                                        m.p. 140-144°                           14  H    4-Cl   H  CH.sub.3    m.p. 191-193°                           15  H    4-Cl   H  C.sub.2 H.sub.5                                                                           m.p. 105-108°                           16  H    4-Cl   H  nC.sub.3 H.sub.7                                                                          m.p. 112-113°                           17  2-Cl 4-Cl   H  CH.sub.3    m.p. 152-154°                           18  2-Cl 4-Cl   H  CH.sub.3    m.p. 124-128°                           19  3-Cl 4-Cl   H  tert.C.sub.4 H.sub.9                                                                      solid                                          20  H    4-Br   CH.sub.3                                                                         CH.sub.3    m.p. 113-115°                           21  2-Cl 4-Cl   H  isoC.sub.3 H.sub.7                                                                        m.p. 92-93°                             22  H    4-Cl   CH.sub.3                                                                         CH.sub.3    m.p. 131-132°                           23  2-Cl 4-Cl   CH.sub.3                                                                         CH.sub.3    solid                                          24  4-t.C.sub.4 H.sub.9                                                                H      H  CH.sub.3    m.p. 162-165°                           25  4-t.C.sub.4 H.sub.9                                                                H      H  C.sub.2 H.sub.5                                                                           solid                                          26  4-t.C.sub.4 H.sub.9                                                                H      H  nC.sub.3 H.sub.7                                                                          solid                                          27  4-t.C.sub.4 H.sub.9                                                                H      H  tert.C.sub.4 H.sub.9                                                                      oil                                            28  H    4-CH.sub.3 O                                                                         H  H                                                          29  H    4-CH.sub.3 O                                                                         H  CH.sub.3    m.p. 182-184°                           30  H    4-CH.sub.3 O                                                                         H  C.sub.2 H.sub.5                                                                           m.p. 106-110°                           31  H    4-CH.sub.3 O                                                                         H  isoC.sub.3 H.sub.7                                                                        m.p. 129-131°                           32  H    4-(CH.sub.3).sub.2 N                                                                 H  CH.sub.3                                                   33  H    4-C.sub.2 H.sub.5 O                                                                  H  CH.sub.3                                                   34  H    4-C.sub.2 H.sub.5 O                                                                  H  isoC.sub.3 H.sub.7                                         35  H    4-NO.sub.2                                                                           H  CH.sub.3                                                   36  H    3-CF.sub.3                                                                           H  CH.sub.3    m.p. 150-151°                           37  H    3-CF.sub.3                                                                           H  C.sub.2 H.sub.5                                            38  H    3-CF.sub.3                                                                           H  H                                                          39  H    3-CF.sub. 3                                                                          CH.sub.3                                                                         CH.sub.3                                                   40  H    H      C.sub.2 H.sub.5                                                                  C.sub.2 H.sub.5                                                                           oil                                            41  H    3-CF.sub.3                                                                           H  nC.sub.4 H.sub.9                                           42  H    H      H  C.sub.6 H.sub.5                                                                           m.p. 132-134°                           43  H    H      H  C.sub.6 H.sub.4 Cl(4)                                                                     m.p. 184-186°                           44  H    H      H  C.sub.6 H.sub.4CH.sub.3 (4)                                                               m.p. 153-154°                           45  H    4-t.C.sub.4 H.sub.9                                                                  H  C.sub.6 H.sub.5                                                                           m.p. 131-133°                           46  3-Cl 4-Cl   H  C.sub.6 H.sub.4 Cl(4)                                      47  3-Cl 4-Cl   H  C.sub.6 H.sub.3 Cl.sub.2 (3,4)                                                            m.p. 210- 213°                          48  3-Cl 4-Cl   H  C.sub.6 H.sub.3 Cl(3)isoC.sub.3 H.sub.7 (4)                                               m.p. 172-175°                           49  H    H      H  C.sub.6 H.sub.4CF.sub.3 (4)                                                               m.p. 188-190°                           50  H    H      H  C.sub.6 H.sub.3 Cl(3)CF.sub.3 (4)                                                         m.p. 207-208°                           51  H    H      H  C.sub.6 H.sub.3 (CF.sub.3).sub.2 (3,5)                                                    m.p. 196-198°                           52  H    H      H  C.sub.6 H.sub.4 F(4)                                                                      m.p. 159-161°                           53  H    H      H  C.sub.6 H.sub.4 CF.sub.3 (3)                                                              m.p. 172-173°                           54  H    4-Cl   H  C.sub.6 H.sub.4 CF.sub.3 (3)                                                              m.p. 187-190°                           55  H    4-Cl   H  C.sub.6 H.sub.4 Cl(4)                                                                     m.p. 204-205°                           56  H    4-Cl   H  C.sub.6 H.sub.3 Cl.sub.2 (3,4)                                                            m.p. 204-205°                           57  H    4-Cl   H  C.sub.6 H.sub.3 Cl(3)isoC.sub.3 H.sub.7 (4)                                               m.p. 150-151°                           58  H    4-Cl   H  C.sub.6 H.sub.5                                                                           m.p. 148-150°                           59  2-Cl 4-Cl   H  C.sub.6 H.sub.3 Cl.sub.2 (3,5)                                                            solid                                          60  4-t.C.sub.4 H.sub.9                                                                H      H  C.sub.6 H.sub.4 Cl(4)                                                                     m.p. 131-133°                           61  4-t.C.sub.4 H.sub.9                                                                H      H  C.sub.6 H.sub.3 Cl.sub.22 (3,4)                                                           m.p. 68-71°                             62  4-t.C.sub.4 H.sub.9                                                                H      H  C.sub.6 H.sub.3 (CF.sub.3).sub.2 (3,5)                                                    m.p. 58-60°                             63  H    3-CF.sub.3                                                                           H  C.sub.6 H.sub.4 (CF.sub.3)(3)                              64  H    3-CF.sub.3                                                                           H  C.sub.6 H.sub.4 (CF.sub.3)(4)                              65  H    4-CH.sub.3 O                                                                         H  C.sub.6 H.sub.3 Cl.sub.2 (3,4)                             66  H    4-C.sub.2 H.sub.5 O                                                                  H  C.sub.6 H.sub.4 CF.sub.3 (3)                               67  H    3-CF.sub.3                                                                           H  C.sub.6 H.sub.5                                                                           m.p. 141-143°                           68  H    3-CF.sub.3                                                                           H  isoC.sub.3 H.sub.7                                                                        m.p. 116-118°                           69  2-Cl 4-Cl   H  C.sub.6 H.sub.5                                                                           m.p. 163-164°                           70  2-Cl 4-Cl   H  C.sub.6 H.sub.3 (CF.sub.3).sub.2 (3,5)                                                    m.p. 110-113°                           71  2-Cl 4-Cl   H  C.sub.6 H.sub.3 Cl.sub.2 (2,4)                                                            m.p. 152-153°                           72  4-t.C.sub.4 H.sub.9                                                                H      H  C.sub.6 H.sub.4 (CF.sub.3)(3)                                                             m.p. 136-140° ;                         __________________________________________________________________________

and also following carbamates of the formula:

    __________________________________________________________________________     ##STR12##                                                                    Comp.                                Physical                                 No. X        R.sub.1                                                                            R.sub.2                                                                             R.sub.5                                                                          R.sub.6   constants                                __________________________________________________________________________    73  CH.sub.3 H    H     H  CH.sub.3  m.p. 97-99°                       74  COCH.sub.3                                                                             H    H     H  CH.sub.3                                           75  H        2-Cl 4-Cl  H  CH.sub.3  m.p. 137°                         76  H        H    H     H  CH.sub.3  m.p. 92-94°                       77  H        H    4-Cl  H  CH.sub.3  m.p. 133-136°                     78  H        H    4-(CH.sub.3).sub.2 N                                                                H  CH.sub.3                                           79  CH.sub.3 H    4-(C.sub.2 H.sub.5).sub.2 N                                                         H  CH.sub.3                                           80  CH.sub.3 3-NO.sub.2                                                                         H     H  CH.sub.3                                           81  H        3-CF.sub.3                                                                         H     H  CH.sub.3                                           82  COOC.sub.2 H.sub.5                                                                     3-CF.sub.3                                                                         H     H  CH.sub.3                                           83  H        4-CH.sub.3 O                                                                       H     H  CH.sub.3                                           84  CH.sub.3 4-CH.sub.3 O                                                                       H     H  CH.sub.3                                           85  H        3-NO.sub.2                                                                         H     H  CH.sub.3                                           86  H        2-NO.sub.2                                                                         H     H  CH.sub.3                                           87  COCH.sub.3                                                                             H    H     H  C.sub.6 H.sub.3 Cl.sub.2 (3,4)                     88  COCH.sub.3                                                                             H    H     H  C.sub.6 H.sub.3 (CH.sub.3).sub.2 (2,4)             89  H        H    H     H  C.sub.6 H.sub.4 Cl(4)                                                                   m.p. 145-146°                     90  H        2-Cl 6-Cl  H  C.sub.6 H.sub.4 Cl(4)                                                                   m.p. 142-144°                     91  CH.sub.3 H    H     H  C.sub.6 H.sub.4 Cl(4)                                                                   m.p. 105-106°                     92  COCH.sub.3                                                                             H    H     H  C.sub.6 H.sub.4 Cl(4)                                                                   m.p. 297-298°                     93  H        H    4-Cl  H  C.sub.6 H.sub.4 Cl(4)                                                                   m.p. 151-152°                     94  H        H    4-Cl  H  C.sub.6 H.sub.5                                                                         m.p. 106-109°                     95  H        H    4-Cl  H  C.sub.6 H.sub.4 CH.sub.3 (3)                                                            m.p. 119-121°                     96  H        H    4-Cl  H  C.sub.6 H.sub.4 F(4)                                                                    m.p. 130-132°                     97  H        H    4-Cl  H  C.sub.6 H.sub.4 NO.sub.2 (4)                       98  COOC.sub.2 H.sub.5                                                                     H    H     H  CH.sub.3                                           99  COOCH.sub.3                                                                            H    H     H  CH.sub.3                                           100 COOt.C.sub.4 H.sub.9                                                                   H    H     H  CH.sub.3                                           101 COOCH.sub.3                                                                            H    4-Br  H  CH.sub.3                                           102 COOC.sub.2 H.sub.5                                                                     H    3-CF.sub.3                                                                          H  CH.sub.3                                           103 COOCH.sub.3                                                                            H    4-Cl  H  C.sub.6 H.sub.5                                    104 CONHCH.sub.3                                                                           H    H     H  CH.sub.3                                           105 CONH.sub.2                                                                             H    H     H  CH.sub.3                                           106 CONHisoC.sub.3 H.sub.7                                                                 H    H     H  CH.sub.3                                           107 CONHCH.sub.3                                                                           H    4-CH.sub.3 O                                                                        H  CH.sub.3                                           108 CONHCH.sub.3                                                                           H    4-Cl  CH.sub.3                                                                         CH.sub.3                                           109 CONHisoC.sub.4 H.sub.9                                                                 H    H     H  CH.sub.3                                           110 CONHt.C.sub.4 H.sub.9                                                                  H    4-Cl  H  CH.sub.3 ;                                         __________________________________________________________________________

and also following carbamates of the formula

    __________________________________________________________________________     ##STR13##                                                                    Comp.                             Physical                                    No. Ar         X     R.sub.5                                                                          R.sub.6   constants                                   __________________________________________________________________________    111 β-naphthyl                                                                          CN    H  CH.sub.3  m.p. 154-158°                        112 β-naphthyl                                                                          CN    C.sub.2 H.sub.5                                                                  C.sub.2 H.sub.5                                                                         m.p. 162-164°                        113 β-naphthyl                                                                          CN    H  tert.C.sub.4 H.sub.9                                  114 β-naphthyl                                                                          CN    H  isoC.sub.3 H.sub.7                                    115 β-naphthyl                                                                          CN    H  C.sub.6 H.sub.4 Cl(4)                                 116 2-furanyl  CN    H  CH.sub.3                                              117 2-furanyl  CN    H  CH.sub.2CCH                                           118 2-furanyl  CN    H  C.sub.6 H.sub.3 Cl.sub.2 (3,4)                        119 2-thienyl  CN    H  CH.sub.3                                              120 2-thienyl  CN    H  C.sub.2 H.sub.5                                       121 2-thienyl  CH.sub.3                                                                            H  CH.sub.3                                              122 (p)C.sub.6 H.sub.5OC.sub.6 H.sub.4                                                       NO.sub.2                                                                            H  CH.sub.3                                              123 (p)C.sub.6 H.sub.5OC.sub.6 H.sub.4                                                       COCH.sub.3                                                                          H  C.sub.6 H.sub.4 CF.sub.3 (4)                          124 H.sub.2 NCO                                                                              CN    H  C.sub.6 H.sub.4 Cl(3)                                                                   m.p. 203-204°                        125 H.sub.2 NCO                                                                              CN    H  C.sub.6 H.sub.4 Cl(4)                                                                   m.p. 201-203°                        126 H.sub.2 NCO                                                                              CN    H  C.sub.6 H.sub.3 Cl.sub.2 (2,5)                                                          m.p. 176-177°                        127 H.sub.2 NCO                                                                              CN    H  C.sub.6 H.sub.4 CF.sub.3 (2)                                                            m.p. 179-183°                        128 H.sub.2 NCO                                                                              CN    H  C.sub.6 H.sub.4 CF.sub.3 (4)                                                            m.p. 170-180°                        129 H.sub.2 NCO                                                                              CN    H  C.sub.6 H.sub.3 Cl(3)CH.sub.3 (4)                                                       m.p. 163-164°                        130 H.sub.2 NCO                                                                              CN    H  CH.sub.3  m.p. 176-177°                        131 H.sub.2 NCO                                                                              CN    H  C.sub.2 H.sub.5                                                                         m.p. 116-120°                        132 H.sub.2 NCO                                                                              CN    H  CH.sub.2 CH.sub.2Cl                                                                     m.p. 141-142°                        133 H.sub.2 NCO                                                                              CN    H  nC.sub.3 H.sub.7                                                                        m.p. 113- 116°                       134 H.sub.2 NCO                                                                              CN    H  isoC.sub.3 H.sub.7                                                                      m.p. 125-126°                        135 H.sub.2 NCO                                                                              CN    H  nC.sub.4 H.sub.9                                                                        m.p. 92-96°                          136 H.sub.2 NCO                                                                              CN    H  C.sub.6 H.sub.5                                                                         m.p. 174-175°                        137 H.sub.2 NCO                                                                              CN    H  C.sub.6 H.sub.3 CF.sub.3 (3)Cl(4)                                                       m.p. 182-183°                        138 C.sub.2 H.sub.5 OOC                                                                      CN    H  C.sub.6 H.sub.4 Cl(4)                                                                   m.p. 147-148°                        139 C.sub.2 H.sub.5 OOC                                                                      CN    H  CH.sub.3  m.p. 101-103°                        140 2-thienyl  CN    H  C.sub.6 H.sub.3 Cl.sub.2 (3,4)                                                          oil                                         141 (5Cl)2-thienyl                                                                           CN    H  CH.sub.3  m.p. 186°                            142 (5Cl)2-thienyl                                                                           CN    H  C.sub.6 H.sub.4 Cl(4)                                                                   m.p. 186°                            143 (5Cl)2-thienyl                                                                           CN    H  C.sub.6 H.sub.3 Cl(4)CF.sub.3 (3)                                                       m.p. 184°;                           __________________________________________________________________________

and also following carbamates of the formula:

    __________________________________________________________________________     ##STR14##                                                                    Comp.                         Physical                                        No. R.sub.4    R.sub.5                                                                          R.sub.6     constants                                       __________________________________________________________________________    144 CH.sub.3 O H  C.sub.6 H.sub.3 CF.sub.3 (3)Cl(4)                                                         m.p. 162°-163°                    145 CH.sub.3 O H  C.sub.6 H.sub.4 CF.sub.3 (3)                                                              m.p. 147°-148°                    146 CH.sub.3 O H  C.sub.6 H.sub.5                                                                           m.p. 149-150°                            147 CH.sub.3 O H  C.sub.6 H.sub.4 NO.sub.2 (3)                                                              m.p. 166-167°                            148 CH.sub.3 O H  C.sub.6 H.sub.4 Cl(3)                                                                     m.p. 162-163°                            149 CH.sub.3 O H  C.sub.6 H.sub.4 Cl(4)                                                                     m.p. 157-158°                            150 CH.sub.3 O H  C.sub.6 H.sub.4 Cl(2)                                                                     m.p. 136-138°                            151 CH.sub.3 O H  C.sub.6 H.sub.4 CF.sub.3 (4)                                                              m.p. 127-128°                            152 CH.sub.3 O H  C.sub.6 H.sub.4 (OC.sub.4 H.sub.9 (i))(4)                                                 m.p. 139-140°                            153 CH.sub.3 O H  C.sub.6 H.sub.3 Cl.sub.2 (3,4)                                                            m.p. 162-163° decomp.                    154 CH.sub.3 O H  C.sub.6 H.sub.3 Cl(3)Br(4)                                                                m.p. 170-171°                            155 CH.sub.3 O H  C.sub.6 H.sub.3 Cl.sub.2 (2,5)                                                            m.p. 164-165°                            156 CH.sub.3 O H  C.sub.6 H.sub.3 CH.sub.3 (2)Cl(3)                                                         m.p. 118-120°                            157 CH.sub.3 O H  C.sub.6 H.sub.3 CH.sub.3 (2)Cl(4)                                                         m.p. 119-120°                            158 CH.sub.3 O H  C.sub.6 H.sub.3 Br(2)CH.sub.3 (4)                                                         m.p. 134-135°                            159 CH.sub.3 O H  C.sub.6 H.sub.3 (CH.sub.3).sub.2 (2,4)                                                    m.p. 115-117°                            160 CH.sub.3 O H  C.sub.6 H.sub.3 Cl(2)NO.sub.2 (4)                                                         m.p. 165-166° decomp.                    161 CH.sub.3 O H  C.sub.6 H.sub.3 Cl.sub.2 (2,4)                                                            m.p. 143-145°                            162 CH.sub.3 O H  CH.sub.3    m.p. 122-123°                            163 CH.sub.3 O H  CH.sub.2 CH.sub.2 Cl                                                                      m.p. 72-74°                              164 C.sub.2 H.sub.5O                                                                         H  C.sub.6 H.sub.5                                                                           m.p. 130-132°                            165 C.sub.2 H.sub.5O                                                                         H  C.sub.6 H.sub.4 Cl(2)                                                                     m.p. 81-82°                              166 C.sub.2 H.sub.5 O                                                                        H  C.sub.6 H.sub.4 Cl(3)                                                                     m.p. 139-141°                            167 C.sub.2 H.sub.5O                                                                         H  C.sub.6 H.sub.4 Cl(4)                                                                     m.p. 156-157°                            168 C.sub.2 H.sub.5O                                                                         H  C.sub.6 H.sub.4 CF.sub.3 (3)                                                              m.p. 117-119°                            169 C.sub.2 H.sub.5O                                                                         H  C.sub.6 H.sub.4 CF.sub.3 (4)                                                              m.p. 136-137°                            170 C.sub.2 H.sub.5O                                                                         H  C.sub.6 H.sub.4 NO.sub.2 (3)                                                              m.p. 145-147°                            171 C.sub.2 H.sub.5O                                                                         H  C.sub.6 H.sub.4 CH.sub.3 (4)                                                              m.p. 121-122°                            172 C.sub.2 H.sub.5O                                                                         H  C.sub.6 H.sub.4 (OC.sub.4 H.sub. 9 (i)(4)                                                 m.p. 127-128°                            173 C.sub.2 H.sub.5O                                                                         H  C.sub.6 H.sub.3 Cl.sub.2 (3,4)                                                            m.p. 160-161°                            174 C.sub.2 H.sub.5O                                                                         H  C.sub.6 H.sub.3 Cl.sub.2 (2,5)                                                            m.p. 136-137°                            175 C.sub.2 H.sub.5O                                                                         H  C.sub.6 H.sub.3 CF.sub.3 (3)Cl(4)                                                         m.p. 141-142°                            176 C.sub.2 H.sub.5O                                                                         H  C.sub.6 H.sub.3 Cl(2)NO.sub.2 (4)                                                         m.p. 133-134°                            177 C.sub.2 H.sub.5O                                                                         H  C.sub.6 H.sub.3 (CF.sub.3).sub.2 (3,5)                                                    m.p. 155-157°                            178 C.sub.2 H.sub.5O                                                                         H  C.sub.6 H.sub.3 CH.sub.3 (2)Cl(4)                                                         m.p. 90-91°                              179 C.sub.2 H.sub.5O                                                                         H  C.sub.6 H.sub.2 Cl.sub.3 (2,4,5)                                                          m.p. 137-139°                            180 C.sub.2 H.sub.5O                                                                         H  CH.sub.3    m.p. 104-106°                            181 C.sub.2 H.sub.5O                                                                         H  CH.sub.2 Cl.sub.2                                                                         m.p. 73-75°                              182 (s)C.sub.4 H.sub.9O                                                                      H  C.sub.6 H.sub.4 Cl(4)                                                                     m.p. 128°-130°                    183 (s)C.sub.4 H.sub.9O                                                                      H  C.sub.6 H.sub.4 CF.sub.3 (3)                                                              m.p. 93°-95°                      184 (s)C.sub.4 H.sub.9O                                                                      H  C.sub.6 H.sub.4 CF.sub.3 (4)                                                              m.p. 109-110°                            185 (s)C.sub.4 H.sub.9O                                                                      H  C.sub.6 H.sub.3 Cl.sub.2 (3,4)                                                            m.p. 140-141°                            186 (s)C.sub.4 H.sub.9O                                                                      H  C.sub.6 H.sub.3 Cl.sub.2 (2,5)                                                            m.p. 100-101°                            187 (s)C.sub.4 H.sub.9O                                                                      H  C.sub.6 H.sub.3 CF.sub.3 (3)Cl(4)                                                         m.p. 126-127°                            188 (s)C.sub.4 H.sub.9O                                                                      H  CH.sub.3    m.p. 80-81°                              189 (s)C.sub.4 H.sub.9O                                                                      H  CH.sub.2 CH.sub.2 Cl                                                                      m.p. 57-59°                              190 CH.sub.2CHCH.sub.2O                                                                      H  C.sub.6 H.sub.5                                                                           m.p. 103-105°                            191 CH.sub.2CHCH.sub.2O                                                                      H  C.sub.6 H.sub.4 Cl(3)                                                                     m.p. 118-120°                            192 CH.sub.2CHCH.sub.2O                                                                      H  C.sub.6 H.sub.4 Cl(4)                                                                     m.p. 131-132°                            193 CH.sub.2CHCH.sub.2O                                                                      H  C.sub.6 H.sub.4 CF.sub.3 (3)                                                              m.p. 106-107°                            194 CH.sub.2CHCH.sub.2O                                                                      H  C.sub.6 H.sub.4 CF.sub.3 (4)                                                              m.p. 121-123°                            195 CH.sub.2CHCH.sub.2O                                                                      H  C.sub.6 H.sub.3 Cl.sub.2 (3,4)                                                            m.p. 126-127°                            196 CH.sub.2CHCH.sub.2O                                                                      H  C.sub.6 H.sub.3 Cl.sub.2 (2,5)                                                            m.p. 130-131°                            197 CH.sub.2CHCH.sub.2O                                                                      H  C.sub.6 H.sub. 2 Cl.sub.3 (2,4,5)                                                         m.p. 124-126°                            198 CH.sub.2CHCH.sub.2O                                                                      H  CH.sub.2 CH.sub.2 Cl                                                                      m.p. 61-63°                              199                                                                                ##STR15## H  C.sub.6 H.sub.4 Cl(4)                                                                     m.p. 141-142°                            200                                                                                ##STR16## H  C.sub.6 H.sub.4 CF.sub.3 (3)                                                              m.p. 94-96°                              201                                                                                ##STR17## H  C.sub.6 H.sub.4 Cl(4)                                                                     m.p. 162-163°                            202                                                                                ##STR18## H  C.sub.6 H.sub.3 CF.sub.3 (3)Cl(4)                                                         m.p. 131-132°                            203                                                                                ##STR19## H  C.sub.6 H.sub.2 Cl.sub.3 (2,4,5)                                                          m.p. 124-126°                            204                                                                                ##STR20## H  CH.sub.3    m.p. 99-101°                             205                                                                                ##STR21## H  C.sub.6 H.sub.4 Cl(3)                                                                     m.p. 136° (decomp.)                      206                                                                                ##STR22## H  C.sub.6 H.sub.3 Cl.sub.2 (3,4)                                                            m. p. 138° (decomp.)                     207                                                                                ##STR23## H  C.sub.6 H.sub.2 Cl.sub.3 (2,4,5)                                                          m.p. 161° (decomp.)                      207a                                                                              CH.sub.3 O CH.sub.3                                                                         CH.sub.3    m.p. 105-106°                            208 CH.sub.3 O H  C.sub.6 H.sub.3 Cl.sub.2 (3,5)                                                            m.p. 156° (decomp.)                      209                                                                                ##STR24## H  C.sub.6 H.sub.3 Cl.sub.2 (3,5)                                                            m.p. 107-108°                            210                                                                                ##STR25## H  C.sub.6 H.sub.3 Cl.sub.2 (3,4)                                                            m.p. 162-163°                            211 CH.sub.3 O H  C.sub.6 H.sub.3 Cl.sub.2 (3,4)                                                            m.p. 162-163°;                           __________________________________________________________________________

and also following carbamates of the formula

    __________________________________________________________________________     ##STR26##                                                                    Comp.                           Physical                                      No. R.sub.5                                                                           R.sub.6  R.sub.9                                                                           R.sub.10   constants                                     __________________________________________________________________________    212 H   C.sub.6 H.sub.3 Cl.sub.2 (3,4)                                                         CH.sub.3                                                                          CH.sub.3   m.p. 153-154°                          213 H   C.sub.6 H.sub.3 CF.sub.3 (3)Cl(4)                                                      CH.sub.3                                                                          CH.sub.3   m.p. 154-156°                          214 H   C.sub.6 H.sub.5                                                                            ##STR27##  m.p. 143-144°                          215 H   C.sub.6 H.sub.5 Cl(2)                                                                      ##STR28##  m.p. 120-123°                          216 H   C.sub.6 H.sub.4 Cl(4)                                                                      ##STR29##  m.p. 142-144°                          217 H   C.sub.6 H.sub.4 CF.sub.3 (4)                                                               ##STR30##  m.p. 160-162°                          218 H   C.sub.6 H.sub.4 Cl.sub.2 (3,4)                                                             ##STR31##  m.p. 153-154°                          219 H   C.sub.6 H.sub.4 CH.sub.3 (4)                                                               ##STR32##  m.p. 133-135°                          220 H   C.sub.6 H.sub.3 CF.sub.3 (3)Cl(4)                                                          ##STR33##  m.p. 140° (decomp.)                    221 H   C.sub.6 H.sub.3 Cl(2)NO.sub.2 (4)                                                          ##STR34##  m.p. 165° (decomp.)                    222 H   C.sub.6 H.sub.3 Cl.sub.3 (2,4,5)                                                           ##STR35##  m.p. 143-145°                          223 H   CH.sub.3                                                                                   ##STR36##  m.p. 113° (decomp.)                    224 H   C.sub.6 H.sub.5                                                                            ##STR37##  m.p. 124-125°                          225     C.sub.6 H.sub.4 Cl(4)                                                                      ##STR38##  m.p. 125-127°                          226 H   C.sub.6 H.sub.3 Cl.sub.2 (3,4)                                                             ##STR39##  m.p. 155-157°                          227 H   C.sub.6 H.sub.3 CF.sub.3 (3)Cl(4)                                                          ##STR40##  m.p. 145° (decomp.)                    228 H   CH.sub.3                                                                                   ##STR41##  m.p. 90° (decomp.)                     229 H   C.sub.3 H.sub.7                                                                        CH.sub.3                                                                          CH.sub.3   m.p. 46-50°                            230 H   CH(CH.sub.3).sub.2                                                                     CH.sub.3                                                                          CH.sub.3   m.p. 62-66°                            231 H   C.sub.4 H.sub.9                                                                        CH.sub.3                                                                          CH.sub.3   oil                                           232 H   C.sub.2 H.sub.5                                                                        CH.sub.3                                                                          CH.sub.3   m.p. 90°                               233 H   CH(CH.sub.3).sub.2                                                                     H   H          m.p. 206-207°                          234 H   CH.sub.3 CH.sub.3                                                                          CH.sub.3   m.p. 72-76°                            235 H   CH.sub.2 CH.sub.2 Cl                                                                   CH.sub.3                                                                          CH.sub.3   m.p. 99-101°                           236 H   C.sub.6 H.sub.4 Cl(3)                                                                      ##STR42##  m.p. 159-161°                          237 H   C.sub.6 H.sub.4 CF.sub.3 (3)                                                               ##STR43##  m.p. 130-132°                          238 H   C.sub.6 H.sub.3 (3)Cl(4)                                                                   ##STR44##  m.p. 176-178°                          239 H   C.sub.6 H.sub.5                                                                        H   C.sub.6 H.sub.4 CF.sub.3 (3)                                                             m.p. 163° (decomp.)                    240 H   C.sub.5 H.sub.4 Cl(4)                                                                  H   C.sub.6 H.sub.4 CF.sub.3 (3)                                                             m.p. 180° (decomp.)                    241 H   C.sub.6 H.sub.3 Cl(3,4)                                                                H   C.sub.6 H.sub.4 CF.sub.3 (3)                                                             m.p. 161° (decomp.)                    242 H   C.sub.6 H.sub.3 CF.sub.3 (3)Cl(4)                                                      H   C.sub.6 H.sub.4 CF.sub.3 (3)                                                             m.p. 169° (decomp.)                    243 H   C.sub.6 H.sub.5                                                                        H   C.sub.6 H.sub.3 Cl.sub.2 (2,4)                                                           m.p. 179° (decomp.)                    244 H   C.sub.6 H.sub.4 Cl(3)                                                                  H   C.sub.6 H.sub.3 Cl.sub.2 (2,4)                                                           m.p. 154° (decomp.)                    245 H   C.sub.6 H.sub.4 Cl(4)                                                                  H   C.sub.6 H.sub.3 Cl.sub.2 (2,4)                                                           m.p. 172° (decomp.)                    246 H   C.sub.6 H.sub.4 CF.sub.3 (3)                                                           H   C.sub.6 H.sub.3 Cl.sub.2 (2,4)                                                           m.p. 165° (decomp.)                    247 H   C.sub.6 H.sub.4 CH.sub.3 (3)                                                           H   C.sub.6 H.sub.3 Cl.sub.2 (2,4)                                                           m.p. 152° (decomp.)                    248 H   C.sub.6 H.sub.3 Cl.sub.2 (3,4)                                                         H   C.sub.6 H.sub.3 Cl.sub.2 (2,4)                                                           m.p. 176° (decomp.)                    249 H   C.sub.6 H.sub.3 Cl.sub.2 (2,5)                                                         H   C.sub.6 H.sub.3 Cl.sub.2 (2,4)                                                           m.p. 185° (decomp.)                    250 H   C.sub.6 H.sub.3 CF.sub.3 (3)Cl(4)                                                      H   C.sub.6 H.sub.3 Cl.sub.2 (2,4)                                                           m.p. 162° (decomp.)                    251 H   C.sub.6 H.sub.3 CH.sub.3 (2)Cl(4)                                                      H   C.sub.6 H.sub.3 Cl.sub.2 (2,4)                                                           m.p. 154° (decomp.)                    252 H   C.sub.6 H.sub.3 CH.sub.3 (2)Cl(3)                                                      H   C.sub.6 H.sub.3 Cl.sub.2 (2,4)                                                           m.p. 140° (decomp.)                    253 H   C.sub.6 H.sub.3 Cl.sub.2 (2,4)                                                         H   C.sub.6 H.sub.3 Cl.sub.2 (2,4)                                                           m.p. 172° (decomp.)                    254 H   C.sub.6 H.sub.9 Cl(3)                                                                  H   C.sub.6 H.sub.3 (CF.sub.3).sub.2 (3,5)                                                   m.p. 165° (decomp.)                    255 H   C.sub.6 H.sub.4 Cl(4)                                                                  H   C.sub.6 H.sub.3 (CF.sub.3).sub.2 (3,5)                                                   m.p. 179° (decomp.)                    256 H   C.sub.6 H.sub.4 CF.sub.3 (3)                                                           H   C.sub.6 H.sub.3 (CF.sub.3).sub.2 (3,5)                                                   m.p. 188° (decomp.)                    257 H   C.sub.6 H.sub.4 Cl(4)                                                                  H   C.sub.6 H.sub.3 Cl(2)NO.sub.2 (4)                                                        m.p. 187° (decomp.)                    258 H   C.sub.6 H.sub.4 CF.sub.3 (4)                                                           H   C.sub.6 H.sub.3 Cl(2)NO.sub.2 (4)                                                        m.p. 198° (decomp.)                    259 H   C.sub.6 H.sub.3 Cl.sub.2 (3,4)                                                         H   C.sub.6 H.sub.3 Cl(2)NO.sub.2 (4)                                                        m.p. 198° (decomp.)                    260 H   C.sub.6 H.sub.3 Cl(2)NO.sub.2 (4)                                                      H   C.sub.6 H.sub.3 Cl(2)NO.sub.2 (4)                                                        m.p. 185° (decomp.)                    261 CH.sub.3                                                                          CH.sub.3                                                                                   ##STR45##  m.p. 104-105°                          262 CH.sub.3                                                                          CH.sub.3 H   C.sub.6 H.sub.3 CH.sub.3 (2)Cl(3)                                                        m.p. 164° (decomp.)                    263 CH.sub.3                                                                          CH.sub.3 H   C.sub.6 H.sub.4 CF.sub.3 (3)                                                             m.p. 115-117°                          264 CH.sub.3                                                                          CH.sub.3 H   C.sub.6 H.sub.3 Cl.sub.3 (2,5)                                                           m.p. 162-164°                          265 CH.sub.3                                                                          CH.sub.3                                                                                   ##STR46##  m.p. 71-72°                            266 H   C.sub.6 H.sub.3 Cl.sub.2 (2,5)                                                         H                                                                                  ##STR47## m.p. 120° (decomp.)                    267 H   C.sub.6 H.sub.4 Cl(3)                                                                  H   CH.sub.2 CHCH.sub.2                                                                      m.p. 154° (decomp.)                    268 H   C.sub.6 H.sub.3 CF.sub.3 (3)Cl(4)                                                      H   CH.sub.2 CHCH.sub.2                                                                      m.p. 175° (decomp.)                    269 H   C.sub.6 H.sub.3 CF.sub.3 (3)CF.sub.3 (4)                                               H   CH.sub.2 CHCH.sub.2                                                                      m.p. 139° (decomp.)                    270 H   C.sub.6 H.sub.4 Cl(4)                                                                  H   CH.sub.2 CHCH.sub.2                                                                      m.p. 170° (decomp.)                    271 H   C.sub.6 H.sub.3 Cl.sub.2 (3,4)                                                         H   CH.sub.2 CHCH.sub.2                                                                      m.p. 164° (decomp.)                    272 H   CH.sub.3 H   CH.sub.2 CHCH.sub.2                                                                      m.p. 111-113°                          273 H   CH(CH.sub.3).sub.2                                                                     H   C.sub.2 H.sub.5                                                                          m.p. 103-105°                          274 H   C.sub.3 H.sub.7                                                                        H   C.sub.2 H.sub.5                                                                          m.p. 78-90°                            275 H   C.sub.4 H.sub.9                                                                        H   C.sub.2 H.sub.5                                                                          m.p. 70.5-74°                          276 H   C.sub.3 H.sub.7                                                                        H   CH.sub.3   m.p. 67-70°                            277 H   CH(CH.sub.3).sub.2                                                                     H   CH.sub.3   m.p. 116-118.5°                        278 H   C.sub.4 H.sub.9                                                                        H   CH.sub.3   m.p. 107-109°                          279 H   CH.sub.2CH.sub.2Cl                                                                     H   CH.sub.3   m.p. 105-106°                          280 H   C.sub.6 H.sub.4 Cl(4)                                                                  H   nC.sub.3 H.sub.5                                                                         m.p. 177-178°                          281 H   C.sub.6 H.sub.3 Cl.sub.2 (3,4)                                                         H   nC.sub.3 H.sub.5                                                                         m.p. 180° (decomp.)                    282 H   C.sub.6 H.sub.3 Cl(3)CH.sub.3 (4)                                                      H   nC.sub.3 H.sub.5                                                                         m.p. 166-167°                          283 H   CH.sub.3 H   nC.sub.3 H.sub.5                                                                         m.p. 124-126°                          284 H   C.sub.6 H.sub.4 Cl(3)                                                                  H   C.sub.6 H.sub.3 Cl.sub.2 (3,5)                                                           m.p. 190° (decomp.)                    285 H   C.sub.6 H.sub.3 CF.sub.3 (3)Cl(4)                                                      H   C.sub.6 H.sub.3 Cl.sub.2 (3,5)                                                           oil                                           286 H   C.sub.6 H.sub.3 Cl.sub.2 (3,4)                                                         H   C.sub.6 H.sub.3 Cl.sub.2 (3,5)                                                           m.p. 173° (decomp.)                    287 H   C.sub.6 H.sub.3 Cl.sub.2 (3)CF.sub.3 (4)                                               H   C.sub.6 H.sub.3 Cl.sub.2 (3,5)                                                           m.p. 182° (decomp.)                    288 H   C.sub.6 H.sub.4 CF.sub.3 (4)                                                           H   C.sub.6 H.sub.3 Cl.sub.2 (3,5)                                                           m.p. 169° (decomp.)                    289 H   CH.sub.3 CH.sub. 2 Cl                                                                  H   H          m.p. 141-142°                          290 H   CH.sub.3 H   CH.sub.3   m.p. 167-168°;                         __________________________________________________________________________

and also the following carbamates of the formula

    ______________________________________                                         ##STR48##                                                                    Comp.                            Physical                                     No.   R.sub.6      R.sub.9                                                                              R.sub.10                                                                             constants                                    ______________________________________                                        291   C.sub.6 H.sub.4 Cl(3)                                                                      H      CH.sub.3                                                                             m.p. 177-178°                         292   C.sub.6 H.sub.4 Cl(3)                                                                      H      C.sub.2 H.sub.5                                                                      m.p. 166-167°                         293   C.sub.6 H.sub.4 Cl(3)                                                                      H      H      m.p. 203° (decomp.)                   294   C.sub.6 H.sub.4 Cl(3)                                                                      CH.sub.3                                                                             CH.sub.3                                                                             m.p. 125-128°                         295   C.sub.6 H.sub.4 Cl(4)                                                                      H      CH.sub.3                                                                             m.p. 198-200°                         296   C.sub.6 H.sub.4 Cl(4)                                                                      H      H      m.p. 203° (decomp.)                   297   C.sub.6 H.sub.4 Cl(4)                                                                      H      C.sub.2 H.sub.5                                                                      m.p. 180° (decomp.)                   298   C.sub.6 H.sub.4 Cl(4)                                                                      CH.sub.3                                                                             CH.sub.3                                                                             m.p. 161-162°                         299   C.sub.6 H.sub.3 CH.sub.3 (4)Cl(3)                                                          H      CH.sub.3                                                                             m.p. 180° (decomp.)                   300   C.sub.6 H.sub.3 CH.sub.3 (4)Cl(3)                                                          CH.sub.3                                                                             CH.sub.3                                                                             m.p. 144-146°                         301   C.sub.6 H.sub.3 CH.sub.3 (4)Cl(3)                                                          H      C.sub.2 H.sub.5                                                                      m.p. 163-163.5°                       302   C.sub.6 H.sub.3 CH.sub.3 (4)Cl(3)                                                          H      C.sub.4 H.sub.9 (n)                                                                  m.p. 142-145°                         303   C.sub.6 H.sub.3 CH.sub.3 (4)Cl(3)                                                          H      H      m.p. 163-166°                         304   C.sub.6 H.sub.3 Cl.sub.2 (3,4)                                                             H      CH.sub.3                                                                             m.p. 195° (decomp.)                   305   C.sub.6 H.sub.3 Cl.sub.2 (3,4)                                                             H      C.sub.2 H.sub.5                                                                      m.p. 175.5°                                                            (decomp.)                                    306   C.sub.6 H.sub.3 Cl.sub.2 (3,4)                                                             H      C.sub.4 H.sub.9                                                                      m.p. 167.5-170°                       307   C.sub.6 H.sub.3 Cl.sub.2 (3,4)                                                             H      H      m.p. 192-193°                         308   C.sub.6 H.sub.3 CF.sub.3 (3)Cl(4)                                                          H      CH.sub.3                                                                             m.p. 198° (decomp.)                   309   C.sub.6 H.sub.3 CF.sub.3 (3)Cl(4)                                                          H      C.sub.2 H.sub.5                                                                      m.p. 185° (decomp.)                   310   C.sub.6 H.sub.3 CF.sub.3 (3)Cl(4)                                                          H      H      m.p. 183° (decomp.)                   311   C.sub.6 H.sub.3 CF.sub.3 (3)Cl(4)                                                          H      C.sub.3 H.sub.7 (n)                                                                  m.p. 172° (decomp.)                   312   C.sub.6 H.sub.3 CF.sub.3 (3)Cl(4)                                                          H      C.sub.4 H.sub.9 (n)                                                                  m.p. 174-177°                         313   C.sub.6 H.sub.3 Cl(3)CF.sub.3 (4)                                                          CH.sub.3                                                                             CH.sub.3                                                                             m.p. 156-158°                         314   C.sub.6 H.sub.3 Cl(3)CF.sub.3 (4)                                                          H      H      m.p. 191° (decomp.)                   315   C.sub.6 H.sub.3 Cl(3)CF.sub.3 (4)                                                          H      CH.sub.3                                                                             m.p. 183-185°                         316   C.sub.6 H.sub.3 Cl(3)CF.sub.3 (4)                                                          H      C.sub.2 H.sub.5                                                                      m.p. 167-169°                         317   C.sub.6 H.sub.3 Cl(3)CF.sub.3 (4)                                                          H      C.sub.4 H.sub.9 (n)                                                                  m.p. 149-150°                         318   C.sub.6 H.sub.4 CF.sub.3 (2)                                                               H      H      m.p. 183° (decomp.)                   319   C.sub.6 H.sub.4 CF.sub.3 (2)                                                               H      CH.sub.3                                                                             m.p. 193° (decomp.)                   320   C.sub.6 H.sub.4 CF.sub.3 (4)                                                               H      H      m.p. 180° (decomp.)                   321   C.sub.6 H.sub.4 CF.sub.3 (4)                                                               H      CH.sub.3                                                                             m.p. 189° (decomp.)                   322   C.sub.6 H.sub.4 CF.sub.3 (4)                                                               CH.sub.3                                                                             CH.sub.3                                                                             m.p. 134-135°                         323   C.sub.6 H.sub.4 Cl(3)                                                                      H      C.sub.3 H.sub.7 (n)                                                                  m.p. 155-157°                         324   C.sub.6 H.sub.4 Cl(4)                                                                      H      C.sub.3 H.sub.7 (n)                                                                  m.p. 170° (decomp.)                   325   C.sub.6 H.sub.4 Cl(4)                                                                      H      C.sub.4 H.sub.9 (n)                                                                  m.p. 170-174°                         326   C.sub.6 H.sub.3 Cl.sub. 2 (3,5)                                                            H      H      m.p. 200° (decomp.)                   327   C.sub.6 H.sub.3 Cl.sub.2 (3,5)                                                             H      C.sub.2 H.sub.5                                                                      m.p. 159° (decomp.)                   328   C.sub.6 H.sub.3 Cl.sub.2 (3,5)                                                             H      CH.sub.3                                                                             m.p. 194° (decomp.)                   329   C.sub.6 H.sub.4 CF.sub.3 (3)                                                               H      CH.sub.3                                                                             m.p. 190° (decomp.)                   330   C.sub.6 H.sub.4 CF.sub.3 (3)                                                               CH.sub.3                                                                             CH.sub.3                                                                             m.p. 109-110°                         331   C.sub.6 H.sub.5                                                                            H      H      m.p. 175° (decomp.)                   332   C.sub.6 H.sub.5                                                                            H      CH.sub.3                                                                             m.p. 162-163.5°                       333   C.sub.6 H.sub.3 Cl.sub.2 (2,3)                                                             H      H      m.p. 156° (decomp.)                   334   CH.sub.3     H      H      m.p. 177° (decomp.)                   335   CH.sub.2 CH.sub.3                                                                          H      H      m.p. 116-120°                         336   CH.sub.3     H      C.sub.2 H.sub.5                                                                      m.p. 119.5-124°                       337   C.sub.3 H.sub.7 (n)                                                                        H      H      m.p. 113-116°                         338   C.sub.6 H.sub.3 Cl(3)CH.sub.3 (4)                                                          H      H      m.p. 163-164°                         339   C.sub.6 H.sub.3 CH.sub.3 (4)Cl(3)                                                          H      CONH.sub.2                                                                           m.p. 197° (decomp.)                   340   C.sub.6 H.sub.3 Cl.sub.2 (3,4)                                                             H      CONH.sub.2                                                                           m.p. 205° (decomp.)                   341   C.sub.6 H.sub.3 CF.sub.3 (3)Cl(4)                                                          H      CONH.sub.2                                                                           m.p. 200° (decomp.)                   342   C.sub.6 H.sub.4 Cl(3)                                                                      H      CONH.sub.2                                                                           m.p. 206° (decomp.)                   343   C.sub.6 H.sub.3 Cl(3)CH.sub.3 (4)                                                          H      CONH.sub.2                                                                           m.p. 197° (decomp.)                   344   C.sub.6 H.sub.3 Cl.sub.2 (3,5)                                                             H      CONH.sub.2                                                                           m.p. 197° (decomp.)                   345   C.sub.6 H.sub.4 CF.sub.3 (3)                                                               H      CONH.sub.2                                                                           m.p. 208° (decomp.)                   346   C.sub.6 H.sub.5                                                                            H      CONH.sub.2                                                                           m.p. 214-215°                         347   C.sub.6 H.sub.3 Cl.sub.2 (2,3)                                                             H      CONH.sub.2                                                                           m.p. 203° (decomp.)                   348   CH.sub.3     H      CONH.sub.2                                                                           m.p. 216° (decomp.);                  ______________________________________                                    

and also following carbamates of the formula:

    ______________________________________                                         ##STR49##                                                                    Comp.                   Physical                                              No.      R.sub.6        constants                                             ______________________________________                                        349      C.sub.4 H.sub.9 (n)                                                                          m.p. 131° (decomp.)                            350      C.sub.3 H.sub.7 (n)                                                                          m.p. 133° (decomp.)                            351      C.sub.3 H.sub.7 (iso)                                                                        m.p. 207° (decomp.)                            352      CH.sub.2CH.sub.2Cl                                                                           m.p. 140-145° (decomp.)                        353      C.sub.3 H.sub.7 (iso)                                                                        m.p. 207° (decomp.)                            ______________________________________                                    

The following (thio)carbonates are produced according to Example 3 or byone of the methods given in the foregoing:

    ______________________________________                                         ##STR50##                                                                    Comp.                         Physical                                        No.    YR.sub.7    R.sub.10   constants                                       ______________________________________                                        354    OC.sub.6 H.sub.5                                                                          H          m.p. 149° (decomp.)                      355    OCH.sub.3   H          m.p. 170° (decomp.)                      356    OC.sub.3 H.sub.7 (iso)                                                                    H          m.p. 171-173°                            357    OCH.sub.3   CH.sub.3   m.p. 97-98.5°                            358    OC.sub.4 H.sub.9 (n)                                                                      H          m.p. 165-167°                            359    OC.sub.3 H.sub.7 (iso)                                                                    CH.sub.3   m.p. 109-110°                            360    O(CH.sub.2).sub.3 CH.sub.3                                                                CH.sub.3   m.p. 75-76°                              361    OCH.sub.3   H          m.p. 120-121°                            362    OCH.sub.3   CH.sub.3   m.p. 73-74°                              363    OC.sub.6 H.sub.5                                                                          CONH.sub.2 m.p. 168° (decomp.)                      364    OCH.sub.3   CONH.sub.2 m.p. 171-172°                            365    SC.sub.2 H.sub.5                                                                          H          m.p. 124-125°                            366    OC.sub.4 H.sub.9 (n)                                                                      CONH.sub.2 m.p. 173° (decomp.)                      367    OC.sub.3 H.sub.7 (iso)                                                                    CONH.sub.2 m.p. 173° (decomp.)                      368    SC.sub.2 H.sub.5                                                                           CONH.sub.2                                                                              m.p. 179° (decomp.)                      369    SC.sub.2 H.sub.5                                                                          CH.sub.3   m.p. 76-78°                              ______________________________________                                    

In the manner described in Example 3 or by one of the methods describedin the foregoing, there can be produced following carbonates of theformula:

    ______________________________________                                         ##STR51##                                                                    Comp.                               Physical                                  No.   R.sub.1                                                                              R.sub.2  G             constants                                 ______________________________________                                        370   H      H        OC.sub.6 H.sub.5                                                                            m.p. 105-108°                      371   H      H        OisoC.sub.3 H.sub.7                                                                         m.p. 108-110°                      372   H      H        OCH.sub.2 CH.sub.2 OCH.sub.3                                                                oil                                       373   H      H        OCH.sub.3     m.p. 108-110°                      374   H      H        OCH.sub.2CCl.sub.3                                                                          solid                                     375   H      H        OC.sub.6 H.sub.4 NO.sub.2 (4)                                                               solid                                     376   H      H        SnC.sub.4 H.sub.9                                       377   H      H        Otert.C.sub.4 H.sub.9                                                                       m.p. 85-86°                        378   H      H        SC.sub.2 H.sub.5                                                                            m.p. 59-62°                        379   3-Cl   4-Cl     SC.sub.2 H.sub.5                                                                            oil                                       380   H      4-Cl     SC.sub.2 H.sub.5                                                                            oil                                       381   2-Cl   4-Cl     SC.sub.2 H.sub.5                                                                            oil                                       382   H      4-CH.sub. 3                                                                            SC.sub.2 H.sub.5                                                                            oil                                       383   H      H        OC.sub.6 H.sub.4 Cl(4)                                  384   H      4-Cl     Osec.C.sub.4 H.sub.9                                    385   H      3-CF.sub. 3                                                                            OCH.sub.3                                               386   H      3-CF.sub. 3                                                                            OC.sub.6 H.sub.5                                        387   H      3-CF.sub. 3                                                                            SC.sub.2 H.sub.5                                        388   H      3-CF.sub. 3                                                                            SCH.sub.3                                               389   H      4-Br     SC.sub.2 H.sub.5                                        390   H      4-CH.sub. 3 O                                                                          OC.sub.6 H.sub.4OCH.sub. 3 (4)                                                              oil                                       391   H      4-CH.sub.3 O                                                                           OC.sub.6 H.sub.4 Cl(4)                                                                      viscous                                   392   H      4-C.sub.C.sub.2 H.sub.5 O                                                              OisoC.sub.3 H.sub.7                                                                         oil;                                      ______________________________________                                    

and also the following carbonates of the formula:

    ______________________________________                                         ##STR52##                                                                    Comp.                                   Physical                              No.   R.sub.1                                                                             R.sub.2   X        G        constants                             ______________________________________                                        393   H     4-(CH.sub.3).sub.2 N                                                                    H        OC.sub.2 H.sub.5                                                                        oil                                  394   H     4-CH.sub.3 O                                                                            H        SC.sub.2 H.sub.5                                                                        oil                                  395   H     4-Cl      COOCH.sub.3                                                                            OCH.sub.3 oil                                  and the following compounds:                                                  No. 396                                                                             ##STR53##                  m.p. 184° (de- comp.)                 No. 397                                                                             ##STR54##                  m.p. 144- 146° (de- comp.)            No.  H.sub.5 C.sub.6C(Cl)NO CONHCH.sub.3                                                                       oil                                          398                                                                           No.  H.sub.5 C.sub.2 OCOC(CN)NOCOSC.sub.2 H.sub.5                                                              oil                                          399                                                                           No.  H.sub.5 C.sub.2 OCOC(CH.sub.3)NOCONHCH.sub.3                                                              m.p.                                         400                              83-85°                                No. 401                                                                             ##STR55##                  m.p. 126° (de- comp.)                 No. 402                                                                             ##STR56##                  m.p. 145° (de- comp.)                 No. 403                                                                             ##STR57##                  m.p. 170° (de- comp.).                ______________________________________                                    

As already mentioned, various methods and techniques are suitable forapplication of the compounds of the formula I for the protection ofcultivated plants against agricultural chemicals:

1. Seed dressing

(a) Dressing of the seed with an active substance formulated as awettable powder by shaking in a vessel until there exists a uniformdistribution over the surface of the seeds (dry dressing). The amount ofactive substance of the formula I used for this purpose is about 10 to500 g (40 g to 2 kg of wettable powder) per 100 kg of seed.

(b) Dressing of the seed with an emulsion concentrate of the activesubstance of the formula I using method (a) (wet dressing).

(c) Dressing by immersion of the seed in a liquor containing 50-3200 ppmof active substance of the formula I for 1-72 hours and, optionally,subsequent drying of the seed (immersion dressing).

The dressing of the seed or the treatment of the germinated seedlingsare naturally the preferred methods of application because the treatmentwith the active substance is directed completely at the target crop.There is used as a rule 10 g to 500 g, preferably 50 to 250 g, of activesubstance per 100 kg of seed, it being possible, depending on the methodused, which method enables also the addition of other active substancesor micronutrients to be made, to deviate either upwards or downwardsfrom the given limiting concentrations (repeat dressings).

2. Application as a tank mixture

A liquid preparation of a mixture of antidote and herbicide (reciprocalquantitative ratio between 1:20 and 5:1 is used, the applied amount ofherbicide being 0.1 to 6 kg per hectare. A tank mixture of this type ispreferably applied before or immediately after sowing, or is worked intothe unsown soil to a depth of 5-10 cm.

3. Application into the seed furrow

The antidote is introduced, as an emulsion concentrate, wettable powderor granulate, into the open sown seed furrow and, after covering of theseed furrow in the normal manner, the herbicide is applied using thepre-emergence process.

Essentially, the antidote can therefore be applied before, togetherwith, or after the herbicide, and its application to the seeds or to thefield can be effected either before or after sowing, or in certain casesalso after germination of the seed.

4. Controlled release of active substance

The active substance in solution is absorbed onto mineral granulatecarriers or onto polymerised granules (urea/formaldehyde), and thematerial is allowed to dry. It is possible if desired to apply a coating(coated granules), which enables the active substance to be released incontrolled amounts over a specific period of time.

The term "seed" within the meaning of the foregoing is not limited tokernels (of cereals, etc.) but encompasses all propagative organs ofcultivated plants. By the term "propagative organs" are meant allgenerative plant parts which can be used for the preparation of thecultivated plants. These parts include kernels, roots, fruits, tubers,rhizomes and stalks, and also emerged plants and seedlings which areintended for transplanting.

It is naturally possible to employ also all other known methods ofapplying active substances. Examples in this connection are given laterin the text.

The compounds of the formula I can be used on their own or together withsuitable carriers and/or other additives. Suitable carriers andadditives can be solid or liquid and they correspond to the substancescommon in formulation practice, such as natural or regenerated mineralsubstances, solvents, dispersing agents, wetting agents, adhesives,thickeners, binders and/or fertilisers.

The content of active substance in commercial compositions is between0.1 to 90%.

The compounds of the formula I can be in the following forms forapplication (the weight-percentage figures in brackets signifyadvantageous amounts of active substance):

solid preparations: dusts and scattering agents (up to 10%), andgranulates (coated granules, impregnated granules and homogeneousgranules) (1 to 80%);

liquid preparations:

(a) water-dispersible concentrates of active substance: wettable powdersand pastes (25 to 90% in the commercial packing, 0.01 to 15% inready-for-use solutions); emulsion concentrates and solutionconcentrates (10 to 50%; 0.01 to 15% in ready-for-use solutions);

(b) solutions (0.1 to 20%) and aerosols.

The active substances of the formula I of the present invention can beformulated for example as follows.

Dust: The following substances are used to produce (a) a 5% dust and (b)a 2% dust:

(a)

5 parts of active substance, and

95 parts of talcum,

(b)

2 parts of active substance,

1 part of highly dispersed silicic acid, and

97 parts of talcum.

The active substances are mixed and ground with the carriers, and inthis form they can be applied by dusting.

Granulate: The following substances are used to produce a 5% granulate:

5 parts of active substance,

0.25 part of epichlorohydrin,

0.25 part of cetyl polyglycol ether,

3.50 parts of polyethylene glycol, and

91 parts of kaolin (particle size 0.3-0.8 mm).

The active substance is mixed with epichlorohydrin and dissolved in 6parts of acetone, and the polyethylene glycol and cetyl polyglycol etherare then added. The solution thus obtained is sprayed onto kaolin, andthe acetone is subsequently evaporated off in vacuo.

Wettable powder: The following constituents are used to produce (a) a70% wettable powder, (b) a 40% wettable powder, (c) and (d) a 25%wettable powder, and (e) a 10% wettable powder:

(a)

70 parts of active substance,

5 parts of sodium dibutylnaphthylsulfonate,

3 parts of naphthalenesulfonic acid/phenolsulfonic acid/formaldehydecondensate 3:2:1,

10 parts of kaolin, and

12 parts of Champagne chalk;

(b)

40 parts of active substance,

5 parts of sodium lignin sulfonate,

1 part of sodium dibutylnaphthalenesulfonate,

54 parts of silicic acid;

(c)

25 parts of active substance,

4.5 parts of calcium lignin sulfonate,

1.9 parts of Champagne chalk/hydroxyethyl cellulose mixture (1:1),

1.5 parts of sodium dibutylnaphthalenesulfonate,

19.5 parts of silicic acid,

19.5 parts of Champagne chalk, and

28.1 parts of kaolin;

(d) 25 parts of active substance,

2.5 parts of isooctylphenoxy-polyoxyethyleneethanol,

1.7 parts of Champagne chalk/hydroxyethylcellulose mixture (1:1),

8.3 parts of sodium aluminium silicate,

16.5 parts of kieselgur, and

46 parts of kaolin, and

(e)

10 parts of active substance,

3 parts of a mixture of the sodium salts of saturated fatty alcoholsulfates,

5 parts of naphthalenesulfonic acid/formaldehyde condensate, and

82 parts of kaolin.

The active substances are intimately mixed in suitable mixers with theadditives, and the mixture is then ground in the appropriate mills androllers. There are obtained wettable powders which have excellentwetting and suspension properties, and which can be diluted with waterto give suspensions of the desired concentration.

Emulsifiable concentrate: The following substances are used to produce a25% emulsifiable concentrate:

25 parts of active substance,

2.5 parts of epoxidised vegetable oil,

10 parts of an alkylarylsulfonate/fatty alcohol polyglycol ethermixture,

5 parts of dimethylformamide, and

57.5 parts of xylene.

Emulsions of the desired concentration can be prepared from theseconcentrates by dilution with water.

POST-EMERGENCE ANTIDOTE TEST IN NUTRIENT SOLUTION General procedure

Plastic flower pots (upper diameter 6 cm), which have a pierced bottom,are filled with Zonolite and the cultivated seeds are sown therein. Thepot is placed into a second transparent plastic flower pot (upperdiameter 7 cm) in which there is 50 ml of water, which rises bycapillary attraction and wets the seeds. From the 5th day the continuousloss of water is compensated with Hewitt nutrient solution. From the15th day, when the cultivated plants are in the 11/2- to 2-leaf stage,there is added to the nutrient solution, made up again to 50 ml, 10 ppmof the antidote to be tested+the amount of herbicide given below. Fromthe 16th day, the loss of liquid is again made up with pure Hewittnutrient solution. During the entire duration of the test, thetemperature is 20°-23° C. with a relative humidity of 60-70%. Threeweeks after addition of the herbicide and antidote, an evaluation ismade on the basis of a linea scale from 1 to 9, with 1 signifying totalplant destruction, and 9 an unimpaired condition of health of thecultivated plants.

TEST VARIANTS

(1) 15 ppm of α-[4-(3,5-dichloropyridyl-2-oxy)-phenoxy]-propionic acidpropargyl thiol ester in wheat of the "Zenith" variety;

(2) 4 ppm of 4-ethylamino-6-tert-butylamino-2-chloro-s-triazine in wheatof the "Zenith" variety;

(3) 2 ppm of α-[4-(p-trifluoromethylphenoxy)-phenoxy]-propionicacid-n-butoxyethyl ester in maize of the "Orla" variety;

(4) 8 ppm of α-[4-(p-trifluoromethylphenoxy)-phenoxy]-propionicacid-n-butoxyethyl ester in sorghum-millet of the "Funk G-522" variety;

(5) 4 ppm of Prometryne=2,4-bis-(isopropylamino)-6-methylthio-s-triazinein sorghum-millet of the "Funk G-522" variety; and

(6) 8 ppm of α-[4-(3,5-dichloropyridyl-2-oxy)-phenoxy]-propionic acidmethyl ester in wheat of the "Zenith" variety.

Compounds of the formula I have a good antidote action in these tests.The following results are given as examples:

    ______________________________________                                                                 Rating of the                                                                 herbicidal effect                                                             (without/with                                        Test variant Compound No.                                                                              antidote)                                            ______________________________________                                        1            91          6/8                                                  6            54          3/7                                                  6            372         2/5                                                  ______________________________________                                    

PRE-EMERGENCE ANTIDOTE TEST IN NUTRIENT SOLUTION

A Hewitt nutrient solution is prepared, which contains the amount ofherbicide given below and 10 ppm of the antidote to be tested.

There is used cultivated seed which could be expected to suffer damagefrom the employed herbicide at the given test concentration, and theseed is sown in granulated Zonolite (=expanded vermiculite) which iscontained in a plastic flower pot having a pierced bottom (upperdiameter 6 cm). This pot is placed into a second tranparent plasticflower pot (upper diameter 7 cm), in which there is about 50 ml of thenutrient solution that has been prepared with herbicide and antidote;this solution then rises by capillary attraction in the filler materialof the smaller pot and wets the seed and germinating plants. The loss ofliquid is made up daily with pure Hewitt nutrient solution to 50 ml.Three weeks after commencement of the test, an evaluation is made on thebasis of a linear scale from 1 to 9, with the rating 1 signifying totalplant destruction, and the rating 9 signifying an unimpaired conditionof health of the plants. The control solution used in a parallel testcontains no antidote addition.

There are used the following:

(1) 4 ppm of Prometryne=2,4-bis-(isopropylamino)-6-methylthio-s-triazinein sorghum-millet of the "Funk G-522" variety;

(2) 4 ppm of 4-ethylamino-6-tert-butylamino-2-chloro-s-triazine in wheatof the "Farnese" variety;

(3) 4 ppm of α-[4-(p-trifluoromethylphenoxy)-phenoxy]-propionicacid-n-butoxyethyl ester in barley of the "Mazurka" variety;

(4) 5 ppm ofMetolachlor=N-(1-methyl-2-methoxy-ethyl)-N-chloroacetyl-2-ethyl-6-methylanilinein sorgum-millet of the "Funk G-522" variety; and

(5) 1 ppm of 2-methoxy-4,6-bis-(γ-methoxy-propylamino)-s-triazine insugar beet of the "Kleinwanzleben" variety.

Compounds of the formula I exhibited in these tests a good antidoteaction. The following results may be given as examples:

    ______________________________________                                                                 Rating of the herbi-                                                          cidal effect (without/                               Test variant                                                                             Compound No.  with antidote)                                       ______________________________________                                        2          73            2/5                                                  4          93            2/5                                                  4          396           2/5                                                  4           4            3/7                                                  4          19            2/6 (with 1 ppm                                                               antidote                                                                      concentration)                                       5          19            2/5                                                  5          36            1/5                                                  3          96            2/5                                                  5          112           1/7 (with 1 ppm                                                               antidote                                                                      concentration)                                       4          52            2/5                                                  4          51            2/5                                                  ______________________________________                                    

ANTIDOTE TEST WITH SEED SOAKING

Rice seeds of the IR 8 variety are saturated during 48 hours withsolutions of the test substances of 10 or 100 ppm concentration. Theseeds are subsequently allowed to dry for about 2 hours, until they nolonger stick together. Rectangular plastic pots (8×8 cm, 10 cm inheight) are filled up to within 2 cm of the edge with sandy loam. Ineach pot is sowed 4 g of seed, and the seed is only very slightlycovered (about the diameter of a seed). The soil is maintained in amoist (not boggy condition). There is then applied either the herbicideN-(1-methyl-2-methoxyethyl)-N-chloroacetyl-2-ethyl-6-methylaniline orN-propoxyethyl-N-chloroacetyl-2,6-diethylaniline in dilute solution andin an amount which converted corresponds to 1.5 kg of active substanceper hectare. An evaluation is made 18 days after planting on the basisof a linear scale from 1 to 9, according to which the rating 1 signifiestotal plant destruction, and the rating 9 an unimpaired condition ofhealth of the plants.

Compounds of the formula I exhibit in this test a good antidote action.The following results may be given as examples:

    ______________________________________                                                          Rating of the herbicidal                                                      effect (without/with                                                Compound No.                                                                            antidote                                                    ______________________________________                                        100 ppm   396         2/5                                                               397         2/5                                                     10 ppm     90         1/4                                                               138         2/5                                                     ______________________________________                                    

PRE-EMERGENCE ANTIDOTE TEST (BASIC TEST) General procedure:

Small flower pots (upper diameter 6 cm) are filled with garden soil,into which the cultivated plants are sown, covered over and lightlypressed down. The substance to be tested as antidote is then sprayed onas a diluted solution (obtained from a wettable powder) in an amountcorresponding to 4 kg of active substance per hectare. The herbicide isafterwards sprayed on in a similar manner. After a standing time of 18days at about 20°-23° C. with 60-70% relative humidity, an evaluation ismade on the basis of a linear scale from 1 to 9, according to which therating 1 signifies total plant destruction, and the rating 9 anunimpaired condition of health of the cultivated plants. Plants withoutantidote protection are used in control tests.

The following are used:

(1) 1.5 kg of active substance per hectare ofα-[4-(p-trifluoromethylphenoxy)-phenoxy]-propionic acid-n-butoxyethylester in maize of the "Orla 264" variety;

(2) 1.5 kg of active substance per hectare ofMetolachlor=N-(1-methyl-2-methoxyethyl)-N-chloroacetyl-2-ethyl-6-methylanilinein sorghum-millet of the "Funk G-522" variety;

(3) 2.0 kg of active substance per hectare ofPrometryne=2,4-bis-(isopropylamino)-6-methylthio-s-triazine in soyabean;

(4) 2.0 kg of active substance per hectare of4-ethylamino-6-tert-butylamino-2-chloro-s-triazine in wheat of the"Farnese" variety;

(5) 4.0 kg of active substance per hectare ofPrometryne=2,4-bis-(isopropylamino)-o-methylthio-s-triazine insorghum-millet of the "Funk G-522" variety;

(6) 2.0 kg of active substance per hectare ofα-[4-(p-trifluoromethylphenoxy)-phenoxy]-propionic acid-n-butoxyethylester in barley of the "Mazurka" variety; and

(7) 1.0 kg; of active substance per hectare ofN-methoxyethyl-N-chloroacetyl-2,6-dimethylaniline in maize of the "Anjou196" variety.

Compounds of the formula I exhibit in these tests a good antidoteaction. The following results are given as examples.

    ______________________________________                                                              Rating of the herbicidal                                                      effect (without/with                                    Test variant                                                                              Comp. No. antidote                                                ______________________________________                                        6           138       4/7                                                     5           398       1/4                                                     4            31       2/4                                                     7            51       2/5                                                     3           378       2/5                                                     ______________________________________                                    

ANTIDOTE ACTION ON TRANSPLANTED RICE WITH SEPARATE APPLICATION (ANTIDOTEPRE-EMERGENCE+HERBICIDE POST-EMERGENCE)

Plastic pots (8×8 cm, 10 cm in height) are filled to within 2 cm of theedge with soil in the boggy-wet condition. The substance to be tested asantidote is sprayed in dilute solution, onto the surface, in an amountcorresponding to 4 kg of active substance per hectare. Rice plants ofthe "IR-8" variety in the 11/2 to 2-leaf stage are transplanted into thepots prepared in this manner. The water level is raised to about 1.5 cmon the next day. Four days after transplanting, there is added to thewater2-ethylamino-4-(1,2-dimethyl-n-propylamino)-6-methylthio-s-triazine ingranular form in an amount which, when converted, corresponds to 0.75 kgof active substance per hectare. The temperature during the duration ofthe test is 26°-28° C., and the relative humidity is 60-80%. Twenty daysafter treatment with the herbicide, an evaluation is made based on alinear scale from 1 to 9, the rating 1 signifying total plantdestruction, and the rating 9 unimpaired condition of health of thecultivated plants. Plants without antidote protection are used incontrol tests.

Compounds of the formula I exhibit in this test a good antidote action.The results below are given as examples.

    ______________________________________                                                   Rating of the herbicidal effect                                    Comp. No.  (without/with antidote)                                            ______________________________________                                        396        3/6                                                                 42        5/7                                                                ______________________________________                                    

I claim:
 1. A method for protecting cultivated plants from being damagedby harmful agricultural chemicals selected from the group consisting oftriazines, haloacetanilides and pyridyloxyphenoxypropionates, whichmethod comprises applying to said plants, to parts thereof or to thelocus of their growth, an antidotally effective amount of a compound ofthe formula ##STR58## in which Ar is naphthyl or ##STR59## wherein R₁ ishydrogen, chlorine, bromine, tert.butyl, methoxy, ethoxy, nitro,trifluoromethyl or dimethylamino,R₂ is hydrogen or chlorine, R₅ ishydrogen, methyl or ethyl, and R₆ is C₁ -C₄ -alkyl, chloroethyl,methoxymethyl, or phenyl optionally substituted by fluorine, chlorine,C₁ -C₃ -alkyl or trifluoromethyl.
 2. The method according to claim 1 inwhich the compound is 3-trifluoromethylphenylglyoxylonitrile oximinomethylcarbamate.
 3. The method according to claim 1 in which thecompound is 3,4-dichlorophenylglyoxylonitrile oximino4'-chlorophenylcarbamate.
 4. The method according to claim 1 in whichthe compound is phenylglyoxylonitrile oximino3'-trifluoromethylphenylcarbamate.
 5. The method according to claim 1 inwhich the compound is 4-chlorophenylglyoxylonitrile oximino4'-chlorophenylcarbamate.
 6. The method according to claim 1 in whichthe compound is 4-tert.butylphenylglyoxylonitrile oximino3',4'-dichlorophenylcarbamate.
 7. The method according to claim 1 inwhich the compound is 2,4-dichlorophenylglyoxylonitrile oximino3',5'-bis(trifluoromethyl)-phenylcarbamate.
 8. The method according toclaim 1 in which the compound is β-naphthylglyoxylonitrile oximinodiethyl carbamate.